Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS4411262 A
Publication typeGrant
Application numberUS 06/336,206
Publication date25 Oct 1983
Filing date31 Dec 1981
Priority date21 Apr 1978
Fee statusPaid
Publication number06336206, 336206, US 4411262 A, US 4411262A, US-A-4411262, US4411262 A, US4411262A
InventorsWulf von Bonin, Ulrich VON Gizycki, Kuno Wagner, Dietmar Schapel
Original AssigneeBayer Aktiengesellschaft
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Constructional material
US 4411262 A
Abstract
The present invention relates to a constructional material which is stable in storage and which is kept under moisture-free conditions and which comprises a substrate and a reactive one-component system which hardens on exposure to air by reaction with moisture. The present invention also relates to a process for the production of a constructional material which is stable in storage.
Images(11)
Previous page
Next page
Claims(30)
What is claimed is:
1. A flexible, workable bandaging or medical material which is stable in storage when kept under moisture-free conditions and which forms a cross-linked rigid self-supporting structure free of extensive foaming upon exposure to sufficient moisture comprising a flexible substrate impregnated or coated with a reactive one-component system consisting essentially of the free isocyanate group bearing reaction products of polyisocyanates selected from the group consisting of
phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate, mixtures of phenylene-1,3- and -1,4-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, mixtures of tolylene-2,4- and -2,6-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenyl- methane-4,4'-diisocyanate, mixtures of diphenylmethane-2,4'- and -4,4'-diisocyanate, naphthylene-1,5-diisocyanate, triphenylmethane-4,4',4"-triisocyanate, polyphenyl-poly- methylene polyisocyanates obtained by aniline-formaldehyde condensation followed by phosgenation, with compounds which contain at least two hydrogen atoms that are reactive with isocyanates selected from the group consisting of polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polyurethanes, polyureas, polyester amides, low molecular weight polyhydroxyl compounds and water.
2. The flexible, workable bandaging or medical splinting material of claim 1 wherein the substrate is a foamed plastic sheet.
3. The flexible workable bandaging or medical splinting material of claim 1 wherein the substrate is a woven or non-woven fabric of organic or inorganic fibers.
4. The flexible, workable bandaging or medical splinting material of claim 1 wherein the substrate is a knitted fabric of organic or inorganic fibers.
5. The flexible, workable bandaging or medical spliting material of claim 1 wherein the reactive one-component system contains less than about 1% by weight of volatile components which can be removed by evaporation at 12 Torr and 20 C. in one hour.
6. The flexible, workable bandaging or medical splinting material of claim 1 wherein the rective one-component system has a viscosity of from about 3,000 to 50,000 cP at 20 C.
7. The bandaging or medical splinting material of claim 1 wherein the reaction product is of an aromatic polyisocyanate with a polyester, polyether, polycarbonate, or low molecular weight polyhydroxyl compound.
8. The bandaging or medical splinting material of claim 7 wherein the polyisocyanate is selected from the group consisting of diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, polyphenyl-polymethylene polyisocyanates of the type obtained by aniline-formaldehyde condensation followed by phosgenation and the reaction partner is a polyether with at least two hydroxyl groups.
9. A process for producing a flexible, workable bandaging or medical splinting material which is stable is storage when kept under moisture-free conditions and which forms a cross-linked rigid self-supporting structure free of extensive foaming upon exposure to sufficient moisture comprising impregnating or coating a flexible substrate under moisture free conditions with a reactive one-component system consisting essentially of the free isocyanate group bearing reaction products of polyisocyanates selected from the group consisting of
phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate, mixtures of phenylene-1,3-and -1,4-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, mixtures of tolylene-2,4- and -2,6- diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, mixtures of diaphenylmethane-2,4'-and -4,4'-diisocyanate naphthylene-1,5-diisocyanate, triphenylmethane-4,4',4"-triisocyanate polyphenyl-polymethylene polyisocyanates obtained by aniline-formaldehyde condensation followed by phosgenation, with compounds which contain at least two hydrogen atoms that are rective with isocyanates selected from the group consisting of polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polyurethanes, polyureas, polyester amides low molecular weight polyhydroxyl compounds and water and subsequently packaging said flexible treated substrate in an air-tight and moisture-free container.
10. A flexible, workable medical splinting or bandaging material enclosed in a moisture-free and moisture-impervious package which is stable in storage and which forms a cross-linked rigid self-supporting planar or hollow structure free of extensive foaming after forming upon exposure to sufficient moisture comprising a flexible substrate impregnated or coated with a reactive one-component system selected from the group consisting of
(a) organic compounds with molecular weights no greater than about 10,000 and containing SiOR-groups, where R is a C1 -C18 alkyl, a C4 -C14 cyclo- alkyl or a phenyl group, which hydrolyze upon exposure to atmospheric moisture and
(b) the free isocyanate group bearing reaction products of polyisocyanates selected from the group consisting of
phenylene-1,3-diisocyanate, phenylene-1,4diisocyanate, mixtures of phenylene-1,3- and -1,4-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, mixtures of tolylene-2,4- and -2,6-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenyl- methane-4,4'-diisocyanate, mixtures of diphenylmethane-2,4'-and -4,4'-diisocyanate, naphthylene-1,5-diiisocyanate, triphenylmethane-4,4',4"-triisocyanate, polyphenyl-poly- methylene polyisocyanates obtained by aniline-formaldehyde condensation followed by phosgenation, with compounds which contain at least two hydrogen atoms that are reactive with isocyanates selected from the group consisting of polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polyurethanes, polyureas, polyester amides, low molecular weight polyhydroxyl compounds and water.
11. The enclosed medical splinting or bandaging material of claim 10 wherein the rective one-component system is based on organic compounds with SiOR-groups.
12. The enclosed medical splinting or bandaging material of claim 10 wherein the reactive one-component system is free isocyanate group bearing rection product.
13. The medical packaging or splinting material of claim 10 or claim 11 or claim 12 in which the impregnated substrate has the property of not substantially changing in flexibility and workability for at least four weeks in the absence of moisture.
14. A flexible, workable bandaging or medical splinting material which is stable in storage when kept under moisture-free conditions and which forms a cross-linked rigid self-supporting structure free of extensive foaming upon exposure to sufficient moisture comprising a flexible substrate impregnated or coated with a reactive one-component system containing no oxycarbonyl isocyanate groups comprising the free isocyanate group bearing reaction product of a polyisocyanate with a compound which contains at least two hydrogen atoms that are reactive with isocyanate groups.
15. The bandaging or medical splinting material of claim 14 wherein the reactive one-component system is a free isocyanate group bearing reaction product of polyisocyanates selected from the group consisting of hexahydrotolylene-2,6-disocyanate, perhydrodiphenyl-methane -2,4'-diisocyanate perhydrodiphenylmethane-4,4'-diisocyanate diphenyl-methane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, mixtures of diphenylmethane-2,4'diisocyanate, tolylene-2,4-diisocyanate tolylene-2,6-diisocyanate, hexamethylene-1,6-diisocyanate, polyphenyl-polymethylene polyisocyanates obtained by aniline-formaldehyde condensation followed by phosgenation with compounds containing at least two hydrogen atoms that are reactive with isocyanates selected from the group consisting of polyesters, polyethers, polycarbonates,low moleculr weight polyhydroxyl compounds and water.
16. The bandaging or medical splinting material of claim 15 wherein the reaction product is of polyisocyanates selected from the group consisting of diphenylmethane-2,4'-diisocyante, diphenylmethane-4,4'-diisocyanate, polyphenyl-polymethylene polyisocyanates obtained by aniline-formaldehyde condensation followed by phosgenation and hexamethylene-1,6-diisocyanate with water or polyethers.
17. A flexible, workable bandaging or splinting material which is storage stable in the absence of moisture and which cures to form a cross-linked rigid structure free of extensive foaming in the presence of atmospheric moisture comprising a flexible substrate impregnated or coated with a free isocyanate group bearing reaction product of a polyisocyanate and a compound which contains at least two hydrogen atoms that are reactive with isocyanate groups, said reaction product containing a catalyst for the reaction of isocyanates with moisture in an amount sufficient to give it a hardening time suitable for a substitute for plaster of paris splinting or bandaging materials and being free of oxycarbonyl isocyanate groups.
18. A medical splinting or bandaging material comprising a flexible, workable substrate impregnated or coated with a reactive system consisting essentially of the free isocyanate group bearing reaction product of an aromatic polyisocyanate and a compound which contains at least two hydrogen atoms that are reactive with isocyanate groups, said reaction product being so formulated that:
(a) it is free of oxycarbonyl isocyanate groups;
(b) it has a viscosity below 50,000 cP at 20 C.;
(c) it contains less than about 1% by weight of volatile components which can be removed by evaporation at 12 Torr and 20 C. in one hour;
(d) said impregnated or coated flexible substrate remains stable and flexible in the absence of moisture;
(e) it will render said impregnated or coated flexible substrate into a cross-linked rigid self-supporting structure free of extensive foaming after forming into a planar or hollw configuration by reaction with water.
19. A process of forming a planar or hollow cross-linked rigid, self-supporting medical splint or bandage comprising;
(a) impregnating or coating a flexible substrate with a free isocyanate group bearing reaction product of an aromatic polyisocyanate with a compound which contains at least two free hydrogen atoms that are reactive with isocyanate groups, said reaction product being storage stable in the absence of moisture, being free pf oxycarbonyl groups; containing less than about 1% by weight of volatile components which can be removed by evaporation at 12 Torr and 20 C. in one hour; and having a viscosity below 50,000 cP at 20 C.;
(b) shaping said impregnated or coated flexible substrate to the desired configuration about the portion of the body to be supported or immobilized; and
(c) reacting said free isocyanate groups with water to yield said cross-linked rigid structure free of extensive foaming.
20. A process of forming a planar or hollow cross-linked, rigid self-supporting medical splint or bandage comprising:
(a) impregnating or coating a flexible substrate with organic compounds with molecular weights no greater than about 10,000 and containing SiOR-groups, where R is a C1 -C18 alkyl, a C4 -C14 cycloalkyl or a phanyl group, which hydrolyze upon exposure to atomspheric moisture, said compounds being storage stable in the absence of moisture;
(b) shaping said impregnated or coated flexible substrate to the desired configuration about the portion of the body to be supported or immobilized; and
(c) reacting said organic compounds with water to yield said cross-linked rigid structure.
21. A medical splinting or bandaging material comprising a flexible, workable substrate impregnated or coated with a reactive system consisting essentially of the free isocyanate group bearing reaction product of:
(a) a polyisocyanate based on the phosgenation product of an aniline formaldehyde condensation; and
(b) a polyether containing at least two hydroxyl groups;
which contains a sufficient amount of a catalyst for the reaction of isocyanate groups with moisture to give it a hardening time suitable for a substitute for plaster of paris splinting or bandaging materials, said reaction product being so formulated that:
(c) it contains less than about 1% by weight of volatile components which can be removed at 12 Torr and 20 C. in one hour;
(d) said impregnated or coated flexible substrate remains formable in the absence of moisture; and
(e) it will render said impregnated or coated flexible substrate into a cross-linked rigid self-supporting structure of comparable mechanical strength to plaster of paris materials free of extensive foaming by reaction with water after forming into a planar or hollow configuration.
22. The medical splinting or bandaging material of claim 21 wherein the polyisocyanate is a mixture of polyphenylpolymethylene polyisocyanates and the 2,2', 2,4' and 4,44' isomers of diphenyl methane diisocyanate obtained from the distillation residue of the phosgenation.
23. The medical splinting or bandaging material of claim 21 wherein the polyisocyanate is the diphenyl methane diisocyanate distillation product of the phosgenation which has been partially carbodiimidized.
24. The medical splinting or bandaging material of claim 22 or claim 23 wherein the polyether contains between 2 and 4 hydroxyl groups.
25. A flexible workable medical splinting or bandaging material enclosed in a moisture-free and moisture impervious package which is stable in storage and which forms a cross-linked rigid self-supporting planar or hollow structure of mechanical strength comparable to plaster of paris materials free of extensive foaming after forming upon exposure to sufficient moisture comprising a flexible substrate impregnated or coated with a reactive one component system consisting essentially of the free isocyanate group bearing reaction product of:
(a) a polyisocyanate based on the phosgenation product of an aniline formaldehyde condensation; and
(b) a polyether containing at least two hydroxyl groups;
said reaction product being so formulated that:
(c) it contains less than about 1% by weight of volatile compounds which can be removed at 12 Torr and 20 C. in one hour;
said impregnated or coated flexible substrate remains formable in the absence of moisture; and
(e) it contains sufficient catalyst for the reaction of isocyanate groups with moisture to give it a hardening time suitable for a substitute for plaster of paris splinting or bandaging materials.
26. The enclosed medical splinting or bandaging material of claim 25 wherein the polyisocyanate is a mixture of polyphenyl-polymethylene polyisocyanates and the 2,2', 2,4' and 4,4' isomers of diphenyl methane diisocyanate obtained from the distillation residue of the phosgenation.
27. The enclosed medical splinting or bandaging material of claim 25 wherein the polyisocyanate is the diphenyl methane diisocyanate distillation product of the phosgenation which has been partially carbodiimidized.
28. The enclosed medical splinting or bandaging material of claim 26 or claim 27 wherein the polyether contains between 2 to 4 hydroxyl groups.
29. A flexible, workable medical splinting or bandaging material enclosed in a moisture-free and moisture-impervious package which is stable in storage and which forms a cross-linked rigid self-supporting planar or hollow structure of comparable mechanical strength to plaster of paris materials free of extensive foaming after forming upon exposure to sufficient moisture comprising a flexible substrate impregnated or coated with a reactive one-component system consisting essentially of the free isocyanate group bearing reaction product of:
(a) an aromatic polyisocyanate; and
(b) a polyhydroxyl compound containing at least two hydroxyl groups;
said reaction product being so formulated that
(c) it contains less than about 1% by weight of volatile compounds which can be removed at 12 Torr and 20 C. in one hour;
(d) said impregnated or coated flexible substrate remains formable in the absence of moisture; and
(e) it contains sufficient catalyst for the reaction of isocyanate groups with moisture to give it a hardening time suitable for a substitute for plaster of paris splinting or bandaging materials.
30. The enclosed medical splinting or bandaging material of claim 29 wherein the polyhydroxyl compound contains between 2 and 4hydroxyl groups.
Description

This application is a continuation of our copending application Ser. No. 898,753, filed Apr. 21, 1978 which in itself is a continuation of application Ser. No. 782,656 filed Mar. 30, 1977, now abandoned, which itself is a continuation in part of our application Ser. No. 684,131 filed May 7, 1976, now abandoned.

FIELD OF THE INVENTION

This invention relates to novel bandanging and stiffening materials and to a process for their production.

BACKGROUND OF THE INVENTION

It is known in the art to steep woven or non-woven webs or knitted goods of various materials in reactive resins, varnishes or polymer solutions and then, after shaping the textiles to solidify them by a hardening reaction (e.g. irradiation with UV light) or by evaporation of the solvent so that they can be used as a dimensionally stable constructional material. It is also known to impregnate woven, non-woven or knitted fabrics with molten high-molecular weight substances and shape then in the hot state and then allow them to solidify by cooling. Lastly, it is known to coat woven or non-woven webs with inorganic dry materials which are stable in storage; these dry materials subsequently setting when moistened with water and thereby imparting strength to the shaped material.

All these processes, however, have disadvantages which stand in the way of economic convenient and, above all, physiologically harmless application. The impregnated webs either still contain volatile monomers or solvents, which may be undesirable for physiological or safety reasons or are unstable in storage. Additionally, the impregnated webs may require moistening with water or solvents, which must subsequently be removed after application by exposure to heat or by the use of mechanical devices which may for example, make it impossible or difficult to use them in contact with human skin.

SUMMARY OF THE INVENTION

It has now been found that constructional materials which are stable in storage before their application and do not have the disadvantages mentioned above can be obtained if a preferably porous and flexible substrate is impregnated and/or coated under air-tight conditions with a single-component reactive system which does not contain any significant quantities of volatile constituents and which is subsequently hardened by moisture upon exposure to air.

The substrate which has been treated in this way is packaged under air-tight conditions and in the absence of moisture and is then stable in storage at temperatures up to about 35 C., preferably up to 25 C. It is only when the liquid-viscous or flexible reactive system is exposed to air that it hardens by reaction with moisture and thereby imparts rigidity, strength and cohesion to the constructional material.

DETAILED DESCRIPTION OF THE INVENTION

This invention therefore relates to a constructional material which is stable in storage and which is kept under moisture-free conditions and which comprises a substrate and a reactive one-component system which hardens on exposure to air by reaction with moisture.

The present application also relates to a process for the production of a constructional material which is stable in storage. The constructional material comprises a substrate impregnated and/or coated with a reactive one-component system which hardens on exposure to air by reaction with moisture, characterized in that the substrate is first treated with the reactive system under moisture-free conditions and then packaged in an air-tight container.

The constructional materials according to the invention are, for example, textile sheets such as (gauze) bandages and twine which are impregnated with the one-component reactive systems, and which, when stored under air-free conditions, are stable in storage.

On removal from the air-tight package, the constructional materials can be applied, for example, as a bandage or other dressing and then harden within a short time. It is not only as bandaging materials that they can be used but also for producing containers, filters, and tubes, for binding constructional elements, for the manufacture of decorative or artistic products, for stiffening purposes or as filling or sealing material for joints and cavities.

The substrates used may be non-porous or, preferably, porous sheets or foams of natural or synthetic materials, e.g. polyurethanes. Woven or knitted fabrics or non-woven webs mad of natural or synthetic organic or inorganic fibrous materials which have an elastic or only slightly elastic character are particularly suitable, for example, leather, cellulose, glass, polyamide, polyolefine, PVC, polyurethane, rubber, acrylic, metal, carbon, polyimide, wool, or polyester fibers. The substrates may, of course, be manufactured either from fibers or from fiber bundles or filaments or foil strips.

Fibrous or filamentary strands or cables, braids etc. are also suitable for use as substrates for the process according to the invention.

The preferred substrates, however, are flexible, sheet-like or strand-like substrates such as foamed plastics sheets, paper, woven glass fabrics, non-woven glass webs and woven, knitted or non-woven webs known per se made of uniform or mixed natural and/or synthetic fibers or filaments such as wool, cotton, aromatic or aliphatic polyamides, polyimides, polyesters, polyacrylonitrile, PVC or polyolefines.

The reactive systems used for the process according to the invention preferably contain less than about 1% by weight of volatile substances which can be removed by evaporation at 12 Torr (1 Torr is equal to 1 mm Hg) and 20 C. in one hour, but they are preferably still tacky and/or have a certain fluidity, shapeability, elasticity, pliability or plasticity so that the substrate impregnated with the reactive system will be in a workable state and have sufficient coherence. the reactive systems should not lose these properties when stored under air-free conditions, but on exposure to air, they should react with moisture to be converted into a rigid, non-tacky or only slightly tacky and no longer fluid and only slightly deformable state so that, for example, a structure made by winding the material according to the invention will have the layers of the winding adhering firmly to each other and will have a stabilized stiff and rigid character.

The reactive systems used in the process according to the invention are generally substances with a viscosity of from about 3,000 to 50,000 cP at 20 C. and, preferably, between about 10,000 and 30,000 cP at 20 C. They contain reactive groups which, optionally in the presence of suitable accelerators or activators, react preferably at ambient temperatures with moisture in the air to form a polymer network or at least undergo an increase in molecular size. These reactive groups may be, for example SiOR-groups or isocyanate groups, where R is a C1 -C18 alkyl, C4 -C18 cycloalkyl or a phenyl group.

One variation of this principle is represented by reactive systems which contain an accelerator or reactant which is masked or not effective on its own, but which reacts with moisture to be converted into an active form in which it is capable of undergoing the hardening reaction. Reactive systems of this kind include, for example systems which contain isocyanate groups and ketimines, the ketimines reacting with the moisture of the air to liberate a reactive amine.

The following are examples of classes of reactive substances suitable for the purpose of the invention which are sufficiently fluid in the absence of air and yet contain less than 1% by weight of volatile components as defined above:

(1) silicones or other organic compounds with molecular weights of up to about 10,000 which contain SiOR-groups, where R is the same as defined immediately above which hydrolize on exposure to atmospheric moisture, whereupon crosslinking or increase in molecular size occurs by condensation of the intermediately formed SiOH-groups;

(2) polyisocyanates or compounds with viscosity below about 50,000 cP at 20 C., preferably polyesters, polyethers, polyamides, polyureas or polyurethanes, which are modified with isocyanate groups in end positions and/or side chains.

Compounds of type (1) have been described, for example, in German Offenlegungsschriften No. 2,155,258; 2,155,259 and 2,155,260, in German Patent Application No. P 22 43 628.8, and in U.S. Pat. Nos. 3,895,043 and 3,856,756, incorporated herein by reference. They are silyl-substituted urea or biuret derivatives which can be prepared by reacting an aminoalkyl silane derivative, of th formula: ##STR1## in which

R represents a C1 -C18 alkyl or C4 -C14 cycloalkyl group or a phenyl group,

R' represents a C1 -C18 alkyl, C4 -C10 cycloalkyl or C6 -C10 aryl group which may be halogenated or cyano-substituted

R" represents a hydrogen atom or a methyl or phenyl group and

a=0, 1 or 2

with a compound which contains uretdione or isocyanate groups; or by reacting a compound of the general formula ##STR2## in which

R, R', R" and a have the meanings specified above and R"' represent hydrogen or a C1 -C18 alkyl, C4 -C14 cycloalkyl or C6 -C14 aryl group which may be halogenated or cyano-substituted and

Q' represents a divalent C1 -C18 -alkyl, C4 -C14 -cycloalkyl or C6 -C14 -aryl or arylalkyl group with a higher molecular weight compound which contains hydroxyl or amino end groups.

The alkoxy silane derivatives used for the process according to the invention are preferably the mixtures described in German Offenlegungsschrift 2,138,943 and U.S. Pat. No. 3,793,253, incorporated herein by reference, because these can be applied solvent-free because of their viscous liquid consistency. The basic constituents of these mixture are 5-silaimidazolidones-(2) of the formula ##STR3## in which

R1 and R2 which may be the same or different, represent alkyl or alkoxy groups or may together represent a bisoxyalkylene group as described in U.S. Pat. No. 3,793,253,

R3 represents hydrogen or an alkyl or aryl group and

R4 represents a divalent (cyclo) aliphatic, araliphatic or aromatic group which may contain hetero atoms.

The compounds mentioned under (2) are preferably used in the present invention and may be either modified or unmodified polyisocyanate or preferably, reaction products of polyisocyanates with compounds which contain at least two hydrogen atoms that are reactive with isocyanates. Apart from compounds which contain amino, thiol or carboxyl groups, the compounds of this kind are preferably water and high-molecular weight or low-molecular weight polyhydroxyl compounds. Suitable higher molecular weight polyhydroxyl compounds are e.g. polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyester amides containing at least two, preferably two to four hydroxyl groups, of the kind known per se for the production both of homogeneous and of cellular polyurethanes.

Suitable polyester with hydroxyl groups are, for example, the reaction products of polyhydric, preferably dihydric alcohols to which trihydric alcohols may be added, and polybasic, preferably dibasic carboxylic acids. Instead of free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof may be used for preparing the polyesters. The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and may be substituted, e.g. with halogen atoms and/or unsaturated. The following are mentioned as examples: succinic acid; adipic acid; suberic acid; azelaic acid; sebacic acid; phthalic acid; isophthalic acid; trimellitic acid; phthalic acid anhydride; tetrahydrophthalic acid anhydride; hexahydrophthalic acid anhydride; tetrachlorophthalic acid anhydride; endomethylene tetrahydrophthalic acid anhydride; glutaric acid anhydride; maleic acid; maleic acid anhydride; fumaric acid; dimeric and trimeric fatty acids such as oleic acid may be mixed with monomeric fatty acids; dimethyl terephthalate and bis-glycol terephthalate. Suitable polyhydric alcohols are e.g. ethylene glycol; propylene-1,2- and -1,3-glycol; butylene-1,4- and -2,3-glycol; hexane-1,6-diol; octane-1,8-diol; neopentyl glycol; cyclohexane dimethanol (1,4-bis-hydroxymethyl cyclohexane); 2-methyl-propane-1,3-diol; glycerol; trimethylolpropane; hexane-1,2,6-triol; butane-1,2,4-triol; trimethylolethane; pentaerythritol; quinitol; mannitol and sorbitol; methyl glycoside; diethylene glycol; triethylene glycol; tetraethylene glycol; polyethylene glycols; dipropylene glycol; polypropylene glycols; dibutylene glycol and polybutylene glycols. The polyesters may contain a proportion of carboxyl groups in end positions. Polyesters of lactones such as ε-caprolactone or hydroxy carboxylic acids such as ω-hydroxycaproic acid may also be used.

The polyethers with at least two, generally two to eight, and preferably, two or three hydroxyl groups which may be used, are also known per se and may be prepared e.g. by polymerizing epoxides such as ethylene oxide, propylene, oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, each with itself, e.g. in the presence of boron trifluoride, or by their addition, either as mixtures or successively, to starting components which contain reactive hydrogen atoms such as water, alcohols or amines, e.g., ethylene glycol, propylene-1,3- or -1,2-glycol, trimethylolpropane, 4,4'-dihydroxy-diphenylpropane, aniline, ammonia, ethanolamine or ethylene diamine. Sucrose polyethers such as those described e.g. in German Auslegeschriften No. 1,176,358 and 1,064,938 may also be used. Polyethers modified with vinyl polymers, as can be obtained e.g. by polymerizing styrene and acrylonitrile in the presence of polyethers (U.S. Pat. No. 3,383,351; 3,304,273; 3,523,093 and 3,110,695 and German Patent Specification No. 1,152,536) are also suitable as are also polybutadienes which contain hydroxyl groups.

Among the polythioethers, there should be particularly mentioned the condensation products of thiodiglycol with itself and/or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols.The products obtained are polythio mixed ethers, polythio ether esters or polythio ether esteramides, depending on the cocomponents.

Suitable polyacetals are e.g. the compounds which can be prepared from glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyl dimethylmethane, hexanediol and formaldehyde. Polyacetals suitable for the purpose of the invention may also be prepared by polymerizing cyclic acetals.

Suitable polycarbonates with hydroxyl groups include those known per se which can be prepared by reacting diols such as propane-1,3-diol, butane-1,4-diol and/or hexane-1,6-diol, diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates such as diphenyl carbonate or with phosgene. Suitable processes for preparing polycarbonates are taught by in Chemistry and Physics of Polycarbonates, by Hermann Schnell, Interscience Publishers, 1964.

Suitable polyester amides and polyamides include the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and mixtures thereof.

Polyhydroxyl compounds which already contain urethane or urea groups and modified or unmodified natural polyols such as castor oil, carbohydrates or starches may also be used. Addition products of alkylene oxides to phenol formaldehyde resins or urea formaldehyde resins are also suitable.

Other examples of higher molecular weight polyhydroxyl compounds may be found e.g. in High Polymers, Volume XVI, "Polyurethanes, Chemistry and Technology" by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pages 32-42 and pages 44-54 and Volume II, 1964, pages 5-6 and 198-199 and in Kunststoff-Handbuch, Volume VII, Vieweg-H,uml/o/ chtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 45 to 71.

Suitable low molecular weight polyhydroxyl compounds are, for example, the compounds mentioned above as suitable starting components for preparing the polyesters.

The polyisocyanates used as one-component reactive systems in the process according to the invention either as such or in the form of their reaction products with the above mentioned polyhydroxyl compounds may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic. A detailed description of these polyisocyanates has been given by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136. The following are mentioned as examples; ethylene diisocyanate; tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; dodecane-1,12-diisocyanate, cyclobutane-1,3-diisocyanate; cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers; 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (German Auslegeschrift No. 1,202,785); hexahydrotolylene-2,4- and -2,6-diisocyanate and any mixtures of these isomers, hexahydrophenylene-1,3- and/or -1,4-diisocyanate; perhydrodiphenylmethane-2,4' and/or -4,4'-diisocyanate;/phenylene-1,3- and -1,4-diisocyanate; tolylene-2,4- and -2,6-diisocyanate and any mixtures of these isomers; diphenylmethane-2,4'-and/or -4,4'-diisocyanate; naphthylene-1,5-diisocyanate; triphenylmethane-4,4',4"-triisocyanate; polyphenyl-polymethylene polyisocyanates which can be obtained by aniline-formaldehyde condensation followed by phosgenation and which have been described e.g. in British Patent Specifications Nos. 874,430, and 848,671; perchlorinated aryl polyisocyanates as described e.g. in German Auslegeschrift No. 1,157,601; polyisocyanates which contain carbodiimide groups as described in German Patent Specification No. 1,092,007; the diisocyanates described in U.S. Pat. No. 3,492,330; polyisocyanates containing allophanate groups according to British Patent Specification No. 994,890, Belgian Patent Specification No. 761,626 and published Dutch Patent Application No. 7,102,524; polyisocyanates which contain isocyanurate groups as described e.g. in German Patent Specification No. 1,022,789; 1,222,067 and 1,027,394 and in German Offenlegungsschriften No. 1,929,034 and 2,004,048; polyisocyanates containing urethane groups as described e.g. in Belgian Patent Specification No. 752,261 or in U.S. Pat. No. 3,394,164; polyisocyanates which contain acylated urea groups according to German Patent Specification No. 1,230,778; polyisocyanates which contain biuret groups as described e.g. in German Patent Specification No. 1,101,394; British Pat. No.889,050 and French Patent Specification No. 7,017,514; the polyisocyanates prepared by telomerization reactions described e.g. in Belgian Patent Specification No. 723,640; polyisocyanates which contain ester groups such as those mentioned e.g. in British Patent Specification No. 956,474 and 1,072,956; U.S. Pat. No. 3,567,763 and in German Patent Specification No. 1,231,688 and reaction products of the above mentioned isocyanates with acetals according to German Patent Specification No. 1,072,385.

Particularly interesting for the process according to the invention are the non-volatile aliphatic and/or aromatic polyisocyanates or corresponding mixed types or various types of residue isocyanates obtained when commercial diisocyanates are processed by distillation. These products may, in addition, contain activators such as organometallic catalysts, for example, tin octoate and tertiary amines.

Polyisocyanates which are obtained by phosgenating aniline-formaldehyde condensates, by trimerizing polyisocyanates or by reaction of polyisocyanates with water or polyols under conditions which give rise to polyisocyanates with urethane, biuret, isocyanurate or allophanate structure are particularly preferred. In the process according to the invention, it is suitable to use mixtures of various such polyisocyanates because the various isocyanate components lower each other's melting points to form mixtures which are liquid at room temperature.

The various isocyanate containing compounds mentioned above are crosslinked by reacting with moisture after application to the constructional material according to the invention. Any extensive foaming by the liberation of carbon dioxide should be avoided, however, in order to guarantee a good mechanical strength of the products.

The substrate is preferably completely impregnated with the one-component reactive system mentioned above but it may also be only coated or wetted on the surface.

In order to achieve special effects with regard to stiffening or permeability of the constructional material, the material may be only partly impregnated or coated. If desired, the material in the form of a woven or non-woven web may be impregnated or coated on one side only so that it will then contain the reactive system only to a certain depth or only on one side. In some cases, it is advisable to impregnate or coat the substrate with other substances before or after it has been treated with the reactive system, for example in order to prevent the reactive system from penetrating too deeply into the substrate, to modify it or to protect the reactive system against mechanical or environmental damage after it has been introduced.

In the process according to the invention, the substrate may be supersaturated with the reaction system so that it also completely fills the gaps between the fibers or intercellular bridges and will exude from the substrate even under light pressure. Alternatively, the substrate may be provided with so little of the reactive system that it only just wets all or only part of the fibers, filaments or other surfaces of the substrate, e.g. the cell walls or filler particles. In the first mentioned case, the end products are substantially impermeable and, in the second case, they are substantially permeable to air, liquids or dust. By suitable choice of the quantities of reactive system used, these properties of the products produced from the constructional materials according to the invention can easily be controlled as desired.

Substrates which have been impregnated or coated according to the invention should preferably still have a certain permeability in order to provide rapid access for the moisture required for hardening the reactive system even into the deep parts of the substrate or of a package produced by winding this material. This can be achieved by, for example, only partly impregnating or coating the substrate, for example, by applying it in the form of a pattern, or by using a sufficiently small quantity of the reactive system.

The impregnation or coating process is carried out with conventional apparatus, for example, by application with a coating knife, steeping the material and then removing excess liquid either on rollers or by centrifuging, or applying the impregnating material by spraying, printing reversal processes or the like. The reactive material may be applied in the form of a solution or, in cases where is has a sufficiently low viscosity at room temperature or at an elevated temperatures, the pure, solvent-free material may be applied. It is preferred to work without any solvent.

Any solvents or other volatile components contained in the reactive systems used according to the invention are, however, removed at the latest after they have been applied to the substrate e.g. by means of a vacuum treatment.

In the process according to the invention, the substrates are generally used in a dried state and treated with the reactive system in sealed apparatus, preferably with the complete exclusion of atmosphere or in a very dry atmosphere, e.g. under nitrogen or noble gases.

After treatment of the constructional materials with the reactive system, they are stored in an air tight and moisture-free environment until they are applied. The constructional materials, which may be in the form of spools, wound packages, rolls or webs or even unformed, are preferably sealed into coated aluminum foils or other foils made of plastics which are very impermeable to moisture.

The materials according to the invention may, of course, also be stored in suitably sealed plastics or metal containers such as cans.

The following reactive systems were used in the examples which serve to explain but not restrict the nature of the new constructional materials:

EXAMPLES

(A) Biuret polyisocyanate which has been prepared according to Example 2 of German Offenlegungsschrift No. 2,308,015 and U.S. Pat. No. 3,903,127 by reacting 11 mols of hexamethylene diisocyanate with 1 mol of tertiary butyl alcohol, at 160-185 C. The product contains 23.3% by weight of isocyanate and has a viscosity of 2800 cP at 20 C. 6 parts by weight of Sn(II)-octoate per 100 parts of polyisocyanate are added before application to the substrate.

(B) Mixture of 30 parts by weight of tolylene-2, 4-diisocyanate (65% of 2,4- and 35% of 2,6-isomer) and 70 parts by weight of the isocyanate residue obtained from the commercial production of this diisocynate. The mixture is dissolved to form a 50% solution in dichloromethane. The solution has an isocyanate content of 12.5%.

By isocyanate residue is meant in this case a material which has been obtained as residue (sump) in the commercial distillation of tolylene diisocyanate and which cannot be distilled at 180 C. at a pressure of 10-15 mm Hg.

(C) Polyester urethane with an average molecular weight of 2900 and --Si--(OC2 H5)3 end groups. The polyester urethane is prepared by reacting an isocyanate-prepolymer from 1 mol of adipic acid/diethylene glycol polyester (hydroxyl number 56) and 2 mols of hexamethylene diisocyanate with 2 mols of N-cyclohexyl-aminomethyl triethoxysilane.

EXAMPLE 1

The following general method of procedure was employed: The reactive material is introduced into a vat in a liquid-viscous form. A substrate web which has been pre-dried in a vacuum at 80 C. is passed through this vat to impregnate it and then freed from excess reactive material by passing it through a pair of rollers. The impregnated substrate web is then passed through a degasification tunnel in which the last residues of volatile constituents are removed at a vacuum of about 1 Torr at 20 C. The impregnated substrate is then wound or rolled up and finally sealed in a polyethylene-coated aluminum foil in a packaging machine. The whole apparatus is arranged in a closed chamber which is filled either with dehydrated air or with dehydrated nitrogen.

This method is used for impregnating gauze bandages, non-woven perlon webs, paper webs, glass fabric webs and webs of polyurethane soft foam foils with the above mentioned reactive materials, A, B and C.

The application of the material will now be described, using as the example gauze bandages which have been treated according to the invention and removed from their sealed package after 4 weeks. They can easily be rolled up to be wound around a mandrel of wire mesh covered with a cotton cloth. The layers of the winding stick together due to the tackiness of the materials. No unpleasant odor or other unpleasant effect due to the chemicals used could be noted. The room in which the material was applied had a relative atmospheric moisture of about 65%.

None of the wound materials prepared in this way were still sticky after 1 hour. After 3 hours, the wound material, impregnated with reactive system A, could be removed from the mandrel and, after about 10 hours, it had reached its final state of firmness. The corresponding times are 0.5 hours and 2.5 hours in the case of B and 0.3 h ours and 2 hours in the case C.

When hardened, the wound materials are stable tubes with air-permeable walls, as can be clearly demonstrated e.g. by blowing tobacco smoke through them.

Wound packages of this kind are suitable, for example, for replacing the conventional rather heavy and impermeable plaster of Paris bandages, especially because they are more permeable to air than conventional bandages.

EXAMPLE 2

A soft polyurethane foam is first prepared as a substrate in known manner by vigorously mixing the following components:

100 parts by weight of a polyether which has been prepared by the addition of 87% by weight of propylene oxide and 13% by weight of ethylene oxide to trimethylolpropane (hydroxyl number 35),

4 parts by weight of water,

0.15 parts by weight of triethylene diamine,

0.35 parts by weight of tin (II) dioctoate,

1 part by weight of foam stabilizer (polyether polysiloxane)

5 parts by weight of monofluorotrichloromethane and

4.8 parts by weight of tolylene diisocyanate (80% of 2,4- and 20% of 2,6-isomer).

A soft polyurethane foam with about 95% of open cells and a density of 25 kp/m3 is obtained. A sheet of this soft foam measuring 310100 cm is impregnated with a solution composed of 50 parts by weight of a sump residue with a molecular weight of about 1000 which contains isocyanate groups from the distallation of a tolylene diisocyanate which has an isomeric ratio of 65 parts by weight of 2,4-isomer and 35 parts by weight of 2,6-isomer, and 50 parts by weight of dichloromethane. The solution of 10 cP when measured in a Hoeppler-viscosimeter at 20 C. When this procedure is employed, the polyurethane matrix swells spontaneously by about 90% of its original volume and, at the same time, the remaining cell walls are burst open.

The excess solution is squeezed off by centrifuging at 600 revs. per min. for 3 minutes. The solvent then still remaining in the foam is removed by applying a vacuum of 0.1 mm Hg at 22 C., the increase in volume being thereby reduced to about 10%. The impregnated foam sheet is rolled up and sealed into a polyethylene coated aluminum foil.

After 6 weeks' storage, the package is opened and the foam web rolled. When exposed to a room temperature of about 20 C. and relative atmospheric humidity of 65%, the soft material becomes hard within about 3 hours. The total increase in weight is about 380%.

Although the invention has been described in detail for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2373802 *6 Jul 194217 Apr 1945Roger AndersonSurgical cast, cast material, and method
US2419358 *15 May 194522 Apr 1947Lovell Chemical CompanySplint and the like
US2582242 *29 Nov 194715 Jan 1952Johnson & JohnsonCast for orthopedic use
US2650212 *20 Aug 194925 Aug 1953Bayer AgAdhesive composition comprising a diisocyanate modified polyester
US2697434 *19 Jul 195221 Dec 1954Du PontSurgical cast and process of forming it
US2785994 *29 Jul 195419 Mar 1957Gen ElectricTreated cellulosic material and method of preparation thereof
US2947307 *20 May 19552 Aug 1960Bayer AgPlastic foam splint
US3015585 *19 Jan 19592 Jan 1962Dow CorningHexafluoroisobutyl substituted silicon compounds
US3124605 *10 Mar 1964 Biuret polyisocyanates
US3301252 *5 Dec 196331 Jan 1967Jr James D MahoneyMethod of applying a polyurethane foam splint
US3307537 *24 Mar 19647 Mar 1967Monroe ReeseOrthopedic cast
US3317481 *24 Jul 19642 May 1967Du PontChemical compositions and process
US3373741 *19 Mar 196519 Mar 1968Army UsaPlastic splint
US3398043 *1 Jul 196520 Aug 1968Dow CorningMethod of bonding silicone elastomers to organic elastomers and product thereof
US3420231 *18 Jul 19667 Jan 1969Johnson & JohnsonThermoplastic cast forming material including an inversely water soluble resin
US3421501 *22 Sep 196514 Jan 1969Leroy E BeightolMethod and application of orthopedic appliances with an ultraviolet curable plastic impregnated bandage
US3490444 *14 Nov 196720 Jan 1970Lester M LarsonThermoplastic splint or cast
US3501330 *22 Oct 196517 Mar 1970Agfa Gevaert NvManufacture of electrophotographic materials
US3572330 *6 Aug 196823 Mar 1971Johnson & JohnsonMethod of treating wounds and immobilizing injured body members with a foamed resin
US3582423 *19 Dec 19661 Jun 1971Wilmington Chem CorpProcess for coating porous substrates
US3617367 *11 Jan 19682 Nov 1971Pacific Vegetable Oil CorpPolyisocyanate-polyamine coating composition
US3630194 *22 May 197028 Dec 1971Johnson & JohnsonOrthopedic bandage
US3635904 *8 Jan 197018 Jan 1972Ici LtdProcess for manufacture of rigid noncellular polyurethane
US3652508 *7 Apr 196928 Mar 1972Gen Latex And Chemical CorpViscosity stable aliphatic polyurethane compositions and method of preparation thereof
US3656475 *5 Mar 197018 Apr 1972Hanrahan James R JrOrthopedic cast and process for applying same
US3683903 *27 Apr 197015 Aug 1972Gen ElectricPlastic cast
US3692023 *20 Jul 197019 Sep 1972Union Carbide CorpFormable orthopedic cast materials, resultant casts and method
US3728206 *23 Nov 197017 Apr 1973Johnson & JohnsonThermoplastic supportive structure
US3792023 *23 Jun 197212 Feb 1974Bayer AgProcess for the production of storagestable polyurethane isocyanates
US3856756 *3 Nov 197224 Dec 1974Bayer AgSilyl substituted urea derivatives and a process for their preparation
US3895043 *2 Nov 197215 Jul 1975Bayer AgSilyl-substituted urea derivatives and a process for their preparation
US3903052 *17 Aug 19732 Sep 1975Bayer AgPolymers containing alkoxysilyl-substituted biuret groups and processes for their preparation
US3903127 *12 Feb 197428 May 1985 Title not available
US3908644 *24 Jun 197430 Sep 1975Allied ChemLightweight orthopedic cast material
US4020832 *24 Dec 19743 May 1977Reichhold Chemicals, Inc.Package and method for preparing orthopedic cast-making materials
US4046744 *28 Jul 19766 Sep 1977Rohm And Haas CompanyThermosetting coatings based on ketoxime-blocked isocyanates and oxazolidines
US4105025 *12 Nov 19768 Aug 1978Yen WangSurgical support
US4131114 *31 Jan 197726 Dec 1978Reichhold Chemicals, Inc.Orthopedic cast
US4134397 *2 Jun 197716 Jan 1979Johnson & JohnsonOrthopedic bandage
US4226230 *27 Mar 19797 Oct 1980Union Carbide CorporationOrthopedic devices, materials and methods
CA625992A *22 Aug 1961Union Carbide & Carbon CorpProcess for treating fibrous glass materials with alkoxysilylmethylamine
DE2357931A1 *20 Nov 197328 May 1975Bayer AgKonstruktionsmaterial
NL6903236A * Title not available
Non-Patent Citations
Reference
1 *Chemical Abstracts 4869r, vol. 74, 1971.
2 *Kunststoffe Band 43, 1953, Heftl 1, Seite 8 along with English Translation, Polyurethanes Chemistry and Technology, Part I, Chemistry, Saunders/Frisch, 1962, pp. 264-266.
3 *Schwab "Light Weight Foam Bandages in Medicine," Plastics Vol. 43, 1953.
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4570622 *24 Oct 198318 Feb 1986Bayer AktiengesellschaftConstructional material
US4638795 *19 Jul 198527 Jan 1987Bayer AktiengesellschaftMaterial for support dressings
US4643909 *7 Oct 198517 Feb 1987Johnson & Johnson Products, Inc.Reinforced casting material
US4667661 *4 Oct 198526 May 1987Minnesota Mining And Manufacturing CompanyCurable resin coated sheet having reduced tack
US4676234 *18 Feb 198630 Jun 1987Bayer AktiengesellschaftMoisture-hardenable bandaging materials
US4681986 *24 Feb 198621 Jul 1987Royston Laboratories, Inc.Splice construction for electrical cable and method for making the same
US4683877 *4 Oct 19854 Aug 1987Minnesota Mining And Manufacturing CompanyOrthopedic casting article and method
US4690842 *20 Jan 19871 Sep 1987Johnson & Johnson Products, Inc.Reinforced casting material
US4705840 *4 Oct 198510 Nov 1987Minnesota Mining And Manufacturing CompanyCatalysts for the curing of a water-curable isocyanate-functional prepolymer
US4741940 *19 May 19863 May 1988Raychem CorporationArticles and methods for protecting substrates
US4748974 *17 Feb 19877 Jun 1988Bayer AktiengesellschaftLaminated dressing
US4767893 *17 Sep 198430 Aug 1988Minnesota Mining And Manufacturing CompanyCable closing
US4770299 *6 Jan 198713 Sep 1988Parker Medical AssociatesRoll form medical bandaging product
US4774937 *6 Nov 19864 Oct 1988Minnesota Mining And Manufacturing CompanyCurable resin coated sheet having reduced tack
US4841958 *5 May 198727 Jun 1989Minnesota Mining And Manufacturing CompanyNonwoven orthopedic casting materials with apertures
US4856502 *22 May 198715 Aug 1989Minnesota Mining And Manufacturing CompanyCurable resin coated sheets having reduced tack
US4869046 *12 Sep 198826 Sep 1989Parker A BruceRoll form medical bandaging product and method of constructing same
US4871845 *6 Aug 19873 Oct 1989Minnesota Mining And Manufacturing CompanyCatalysts for the curing of a water-curable isocyanate-functional prepolymer
US4888225 *3 Jun 198819 Dec 1989Minnesota Mining And Manufacturing CompanyResin-impregnated foam materials and methods
US4893617 *7 Aug 198716 Jan 1990Minnesota Mining And Manufacturing CompanyResilient semi-rigid orthopedic support devices
US4899738 *12 Sep 198813 Feb 1990Parker A BruceRoll form medical bandaging product
US4946726 *18 Feb 19877 Aug 1990Minnesota Mining And Manufacturing CompanyOrthopedic splinting articles and methods
US4947839 *18 Aug 198814 Aug 1990CarapaceOrthopedic casting material having reduced tack and reduced slip
US4968542 *3 Sep 19866 Nov 1990Minnesota Mining And Manufacturing CompanyCurable material for semi-rigid resilient orthopedic support
US5002047 *4 Sep 198726 Mar 1991Minnesota Mining And Manufacturing CompanyOrthotic pads and methods
US5003970 *8 Feb 19902 Apr 1991Parker Medical AssociatesRoll form medical bandaging product, method of constructing same and container for roll form bandaging product
US5007418 *9 Nov 198916 Apr 1991Minnesota Mining And Manufacturing CompanyResilient semi-rigid orthopedic support devices
US5014403 *7 Feb 199014 May 1991Johnson & Johnson Orthopaedics, Inc.Method of making a stretchable orthopaedic fiberglass casting tape
US5052380 *7 Jul 19891 Oct 1991Minnesota Mining And Manufacturing CompanyColored orthopedic resins and orthopedic casting materials incorporating same
US5064653 *29 Mar 198812 Nov 1991Ferris Mfg. Co.Hydrophilic foam compositions
US5065752 *28 May 199119 Nov 1991Ferris Mfg. Co.Hydrophilic foam compositions
US5195945 *25 Mar 199123 Mar 1993Minnesota Mining And Manufacturing CompanyOrthotic pads and methods
US5203764 *27 Nov 199120 Apr 1993Minnesota Mining And Manufacturing CompanyFoam pads useful in wound management
US5206064 *18 Apr 199127 Apr 1993Minnesota Mining And Manufacturing CompanyCurable resins with solid supported antifoaming agents
US5225513 *8 Aug 19916 Jul 1993Minnesota Mining And Manufacturing CompanyCasting article and composition
US5244997 *4 Sep 199214 Sep 1993Minnesota Mining And Manufacturing CompanyCatalysts, catalysis method, casting article, and method of orthopedic casting
US5256134 *11 Sep 198926 Oct 1993Smith & Nephew PlcConformable bandage
US5273802 *7 Jul 198928 Dec 1993Minnesota Mining And Manufacturing CompanyOrthopedic casting materials having superior lamination characteristics due to napped surface
US5346939 *25 Jan 199313 Sep 1994Minnesota Mining And Manufacturing CompanyWater curable resin compositions
US5353486 *13 Nov 199211 Oct 1994Minnesota Mining And Manufacturing CompanyNarrow fiberglass knit tape
US5354259 *25 Jan 199311 Oct 1994Minnesota Mining And Manufacturing CompanyMicrofiber fillers for orthopedic casting tapes
US5364693 *25 Jan 199315 Nov 1994Minnesota Mining And Manufacturing CompanyOrthopedic support materials
US5370927 *25 Oct 19936 Dec 1994Minnesota Mining And Manufacturing CompanyWet compacting of fabrics for orthopedic casting tapes
US5382445 *25 Jan 199317 Jan 1995Minnesota Mining And Manufacturing CompanyMechanically compacted fabrics for orthopedic casting tapes
US5403267 *14 Apr 19934 Apr 1995Smith & Nephew PlcOrthopedic bandages with low modulus filaments
US5405643 *25 Jan 199311 Apr 1995Minnesota Mining And Manufacturing CompanyMicrocreping of fabrics for orthopedic casting tapes
US5409448 *15 Jul 199325 Apr 1995Parker Medical AssociatesEasily removed tubular cast assembly, and method for removing a cast
US5415622 *21 Dec 199316 May 1995Parker Medical AssociatesEasily removed tubular cast assembly and method for removing a cast
US5423735 *16 Apr 199313 Jun 1995Minnesota Mining And Manufacturing CompanyOrthopedic cast composed of an alkoxysilane terminated resin
US5449550 *1 Sep 199412 Sep 1995Minnesota Mining And Manufacturing CompanyMechanically compacted fabrics for orthopedic casting tapes
US5454780 *2 Jun 19943 Oct 1995Parker Medical AssociatesCustom body protective device with variable reenforcement
US5455060 *25 Oct 19933 Oct 1995Minnesota Mining And Manufacturing CompanyCompacted fabrics for orthopedic casting tapes
US5456658 *15 Sep 199410 Oct 1995Parker Medical AssociatesCustom-fitting body part protector with cure-retarding storage system, method of constructing a body part protector, and method of custom-fitting a body part protector
US5470306 *23 Feb 199428 Nov 1995Kirschner Medical CorporationMedical bandaging article and packaging system
US5474522 *24 May 199412 Dec 1995Minnesota Mining And Manufacturing CompanyMicrofiber fillers for orthopedic casting tapes
US5476440 *19 Jul 199419 Dec 1995Carapace, Inc.Orthopedic bandage with lubricious core
US5480376 *15 Sep 19942 Jan 1996Parker Medical AssociatesCustom body protective pad with cure-retarding storage system
US5498232 *1 Sep 199412 Mar 1996Minnesota Mining And Manufacturing CompanyMicrocreping of fabrics for orthopedic casting tapes
US5507079 *2 Aug 199416 Apr 1996Minnesota Mining And Manufacturing CompanyNarrow fiberglass knit tape
US5512354 *25 Jan 199330 Apr 1996Minnesota Mining And Manufacturing CompanyFabric backing for orthopedic support materials
US5520621 *25 Jul 199428 May 1996Carapace, Inc.Water-permeable casting or splinting device and method of making same
US5540652 *9 Feb 199530 Jul 1996Minnesota Mining And Manufacturing CompanyOrthopedic cast composed of an alkoxysilane terminated resin
US5540982 *19 Jan 199430 Jul 1996Minnesota Mining And Manufacturing CompanyFabric backing for orthopedic support materials
US5553366 *27 Mar 199510 Sep 1996Minnesota Mining And Manufacturing CompanyVibration compacted fabrics for orthopedic casting tapes
US5584800 *21 Feb 199517 Dec 1996Minnesota Mining And Manufacturing CompanyMethod of enclosing a body member using an apertured, extruded sheet
US5593628 *24 May 199514 Jan 1997Minnesota Mining And Manufacturing CompanyMethod of making an orthopedic casting article comprising an apertured, extruded sheet
US5603691 *16 Apr 199318 Feb 1997Minnesota Mining And Manufacturing CompanyMethod of using water soluble films in curable casting tapes
US5620095 *10 Mar 199515 Apr 1997Minnesota Mining And Manufacturing CompanyOrthopedic casting material and hermetic package
US5637077 *30 Oct 199510 Jun 1997Smith & Nephew Casting, Inc.Custom-molded ankle brace
US5641560 *16 Jan 199624 Jun 1997Minnesota Mining And Manufacturing CompanyNarrow fiberglass knit tape
US5658650 *31 May 199519 Aug 1997Minnesota Mining And Manufacturing CompanyCompacted fabrics for orthopedic casting tapes
US5716661 *5 Jun 199510 Feb 1998Minnesota Mining And Manufacturing CompanyMethod of making a light weight orthopedic casting tape
US5718925 *15 Nov 199517 Feb 1998Ossur Hf.Apparatus for making a prosthesis socket
US5725487 *7 Jun 199510 Mar 1998Johnson & Johnson Professional, Inc.Orthopedic casting tape
US5738639 *3 May 199614 Apr 1998Clinitex Medical CorporationTreated core for facilitating orthopedic casting
US5744528 *15 May 199528 Apr 1998Minnesota Mining And Manufacturing CompanyAlkoxysilane terminated resin and methods of making and using same
US5755678 *13 Oct 199526 May 1998Parker; A. BruceCustom-fitted body protective device with variable reenforcement
US5800899 *5 Jun 19951 Sep 1998Minnesota Mining And Manufacturing CompanyOrthopedic casting material having improved wet strength
US5807292 *24 Jun 199615 Sep 1998Minnesota Mining And Manufacturing CompanyOrthopedic casting article having soft and hard regions
US5823978 *24 Apr 199620 Oct 1998Clinitex Medical CorporationLow modulus synthetic fiber casting system
US5868693 *10 Sep 19979 Feb 1999Parker Medical Associates Limited PartnershipCustom-fitted athletic ankle brace
US5885234 *27 May 199823 Mar 1999Minnesota Mining And Manufacturing CompanyOrthopedic casting material having improved wet strength
US5888231 *8 Oct 199730 Mar 1999Minnesota Mining And Manufacturing CompanyCustom-molded liner for artificial limb socket
US5916928 *5 Jun 199529 Jun 1999Ferris CorporationPolymer-based porous foam
US5971729 *17 Feb 199826 Oct 1999Ossur HfDevice for making prosthetic residual limb socket
US5972036 *17 Feb 199826 Oct 1999Ossur Usa Inc.Process and apparatus for making prosthesis socket and prosthesis socket made thereby
US5976610 *4 Nov 19972 Nov 1999Minnesota Mining And Manufacturing CompanyMethod of making a light-weight orthopedic casting article
US5980576 *27 Feb 19989 Nov 1999Graf; Peter M.Method of providing prosthetic sockets and temporary prosthetic socket
US5984088 *4 Feb 199716 Nov 19993M Innovative Properties CompanyEasy open package and method of making same
US5997492 *19 Dec 19977 Dec 19993M Innovative Properties CompanyOrthopedic casting articles containing backings having water soluble binders
US6027465 *5 Jun 199522 Feb 2000Minnesota Mining And Manufacturing CompanyMethod of immobilizing a body member using a composite article
US6030355 *12 Nov 199729 Feb 20003M Innovative Properties CompanyOrthopedic support material containing a silicate
US6074354 *6 May 199613 Jun 20003M Innovative Properties CompanyOrthopedic casting article comprising an apertured, extruded sheet
US6077240 *15 Mar 199520 Jun 20003M Innovative Properties CompanyWater soluble films used in synthetic casting tapes
US6100206 *4 Nov 19978 Aug 20003M Innovative Properties CompanyLight-weight orthopedic casting article
US6126626 *9 Feb 19993 Oct 2000Parker Medical Associates Limited PartnershipCustom-fitted athletic ankle brace
US6128777 *29 Jul 199910 Oct 2000Parker Athletic Products, LlcCustom-fitted batter's forearm protector
US6131195 *29 Jul 199917 Oct 2000Parker Athletic Products, LlcCustom-fitted batter's lower leg protector
US6132835 *5 Jun 199517 Oct 2000Minnesota Mining And Manufacturing CompanyComposite casting tape
US6134720 *29 Jul 199924 Oct 2000Parker Athletic Products, LlcShin guard with enhanced tibial protection
US6159877 *13 Feb 199812 Dec 20003M Innovative Properties CompanyFabric backing for orthopedic support materials
US62694857 Jun 20007 Aug 2001Parker Athletic Products, LlcCustom-fitted batter's lower leg protector
US638623631 May 200014 May 2002Air Logistics CorporationMethod of prestressing and reinforcing damaged cylindrical structures
US641670321 Sep 19999 Jul 2002Ossur HfMethod for making prosthetic residual limb socket
US659593811 Aug 199822 Jul 20033M Innovative Properties CompanyArticle having soft and hard regions
US66737271 Feb 20016 Jan 2004Ebi, L.P.Orthopedic casts with controlled flexibility
US697443021 Jan 200313 Dec 2005Esn Medical, Inc.Knitted substrate with high and low tenacity yarns for use in bandaging product, bandaging product and method of forming same
US724087621 Apr 200510 Jul 2007Ossur, HfDispenser box
US783763716 Apr 200723 Nov 2010Ebi, LlcSafety cast
US79851929 Sep 200526 Jul 2011Fastform Research LimitedGeometrically apertured protective and/or splint device comprising a re-mouldable thermoplastic material
US84196681 Apr 201016 Apr 2013Donald SpectorCompact package for an orthopedic cast
EP0172379A1 *10 Jul 198526 Feb 1986Bayer AgMaterial for orthopaedic bandages
EP0276118A2 *19 Jan 198827 Jul 1988Johnson & Johnson Hospital Services, Inc.Ravel-free orthopaedic casting tapes
EP0564246A1 *30 Mar 19936 Oct 1993A. Bruce ParkerCustom body protective device
EP0693944A1 *22 Feb 199431 Jan 1996Minnesota Mining And Manufacturing CompanyNovel casting tapes and resins and processes therefor
EP0701845A114 Sep 199520 Mar 1996Parker Medical AssociatesCustom body protective pad with cure-retarding storage system
EP0701846A114 Sep 199520 Mar 1996Parker Medical AssociatesCustom-fitting body part protector with cure-retarding storage system and methods of constructing and applying said protector
EP0815760A217 Mar 19947 Jan 1998Minnesota Mining And Manufacturing CompanyOrthopedic casting material
EP0970708A1 *22 Feb 199412 Jan 2000Minnesota Mining And Manufacturing CompanyNovel casting tapes and resins and processes therefor
EP1348798A1 *27 Mar 20031 Oct 2003Depuy Products, Inc.Surface protection material and method
EP1944334A1 *15 Jan 200816 Jul 2008SoudalPressurised container containing a foaming composition for elastic foam
WO1996039201A1 *26 Apr 199612 Dec 1996Minnesota Mining & MfgOrthopedic casting material having improved wet strength
WO2002045630A25 Dec 200113 Jun 2002Bsn Medical IncCustom-formable knee immobilizer product, knee immobilizer and method
WO2009094037A130 Jan 200830 Jul 2009Bsn Medical IncMedical bandage cover, medical bandage, and medical bandaging product
WO2013090245A111 Dec 201220 Jun 2013Bsn Medical, Inc.Knitted substrate for use in medical bandaging product and bandaging product
Classifications
U.S. Classification602/8, 523/111, 428/423.1, 428/425.6, 264/137, 428/447
International ClassificationC08G18/10, A61L15/12, C08G18/30, C08G18/48
Cooperative ClassificationC08G18/10, C08G18/307, A61L15/12, C08G18/4837
European ClassificationC08G18/10, A61L15/12, C08G18/30D5, C08G18/48F5
Legal Events
DateCodeEventDescription
26 Mar 2003ASAssignment
Owner name: ZIMMER ORTHOPAEDIC SURGICAL PRODUCTS, INC., OHIO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ZIMMER, INC.;REEL/FRAME:013845/0422
Effective date: 20020628
Owner name: ZIMMER ORTHOPAEDIC SURGICAL PRODUCTS, INC. 200 WES
Owner name: ZIMMER ORTHOPAEDIC SURGICAL PRODUCTS, INC. 200 WES
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ZIMMER, INC. /AR;REEL/FRAME:013845/0422
25 Apr 1995FPAYFee payment
Year of fee payment: 12
22 Mar 1991FPAYFee payment
Year of fee payment: 8
24 Nov 1986FPAYFee payment
Year of fee payment: 4
16 Jul 1985B1Reexamination certificate first reexamination
16 Oct 1984RRRequest for reexamination filed
Effective date: 19840823